The present invention discloses two polyoxoanion supported metal complexes found to be useful in olefin hydrogenation. The complexes are novel compositions of matter which are soluble in organic solvents. In particular, the compositions of matter comprise Ax [Ln Ir(I) ·X2 M15 M'3 O62 ]x- and Ay [Ln Ir(I) ·X2 M9 M'3 O40 ]y- where L is a ligand preferably chosen from 1,5-cyclooctadiene (COD), ethylene, cyclooctene, norbornadiene and other olefinic ligands; n=1 or 2 depending upon the number of double bonds present in the ligand L; X is a "hetero" atom chosen from B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu; M is either W or Mo; M' is preferably Nb or V but Ti, Zr, Ta, hf are also useful; and A is a countercation preferably selected from tetrabutyl ammonium and alkali metal ions.
|
8. A hydrogenation catalyst precursor which comprises
A+6 [Ln Ir.SiW9 Nb3 O40 ]8- wherein A is a countercation selected from the group consisting of tetraalkyl ammonium cations or alkali metal cations, L is an olefinic ligand, and n is 1 or 2. 7. A hydrogenation catalyst precursor which comprises
A+8 [Ln Ir.P2 W15 Nb3 O62 ]8- wherein A is a countercation selected from the group consisting of tetraalkyl ammonium cations or alkali metal cations, L is an olefinic ligand, and n is 1 or 2. 1. A catalyst precursor which comprises:
Ax[Ln Ir(1).X2 M15 M'3 O62 ]x- wherein A is a countercation; L is an olefinic ligand or dioxygen; Ir(1) is monovalent iridium; n=1 or 2; X is a hetero atom selected from the group consisting of B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu; M=W or Mo; M'=Nb, V, Ti, Zr, Ta or hf; and, x<15. 4. A catalyst precursor which comprises:
Ay [Ln Ir(1).X2 M9 M'3 O40]y- wherein A is a countercation; L is an olefinic ligand or dioxygen; Ir(1) is monovalent iridium; n=1 or 2; X is a hetero atom selected from the group consisting of B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu; M=W or Mo; M'=Nb, V, Ti, Zr, Ta or hf; and, y<15. 10. A hydrogenation catalyst prepared by
a) reacting (Bu4 n)7 SiW9 Nb3 O40 with [Ir(COD)(CH3 CN)2 ]BF4 under nitrogen in the presence of acetonitrile to obtain (Bu4 n)6 [Ir(COD).SiW9 Nb3 O40 ] and Bu4 NBF4 ; and b) treating (Bu4 n)6 [Ir(COD).SiW9 Nb3 O40 ] with acetone at 40 psig H2, 25°C for up to two hours to obtain (BU4 n)6 (L'n Ir.SiW9 Nb3 O40 ] and cyclooctane where L' is an olefinic ligand and n is 1 or 2.
9. A hydrogenation catalyst precursor prepared by
a) reacting (Bu4 n)9 P2 W15 Nb3 O62 with [Ir(COD)(CH3 CN)2 ]BF4 under nitrogen in the presence of acetonitrile to obtain (Bu4 n)8 [Ir(COD).P2 W15 Nb3 O62 ]+Bu4 NBF4 ; and b) treating (Bu4 n)8 ]Ir(COD).P2 W15 Nb3 O62 ] with acetone at 40 psig H2, 25°C for up to two hours to obtain [(Bu4 n8 [L'n Ir.P2 W15 Nb3 O62 ]] (Bu4 n)8 [L'n Ir.P2 W15 Nb3 O62 ]+cyclooctane where L'is an olefinic ligand and n is 1 or 2.
11. The hydrogenation catalyst precursor of
12. The hydrogenation precursor of
|
|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
1. Technical Field
This invention relates generally to organometallic complexes and their use in homogeneous catalysis, and more specifically to novel covalently bonded iridium-heteropolyanion species which are used as hydrogenation catalysts.
2. Background of the Invention
Catalysis by a bulk, oxide-supported metal two phase system, commonly referred to as heterogeneous catalysis, while generally producing high turnover frequencies and ease of product/catalyst separation, is plagued by a lack of chemical selectivity in addition to analytical difficulties in determining the chemical composition of the active site(s) as well as mechanistic details. Attempts to circumvent these short comings have primarily focused on chemically binding a discrete, well characterized organometallic moiety to a support, typically a polymer or silica substrate, thereby making the previously soluble organometallic complex insoluble and atomically dispersed. However, the usefulness of these "heterogenized" complexes as catalysts is limited by the same analytical difficulties associated with characterizing and doing mechanistic studies on bulk solid, two phase catalyst systems.
One recent report discloses a hydrogenation catalyst employing Rhodium and selected heteropolyanions (specifically Li4 SiW12 O40 and Li4 SiMo12 O40) (Urabe, K. et al., Chem. Lett., 1985, 1595). However, such polyoxoanions have zero surface charge and therefore are unable to covalently bond to and support an organometallic. Therefore, this polyoxoanion system is considered less desirable because it will not hinder Rh(0) formation in a Cl- and PPh3 -free system, nor will it prevent attachment of RhI) to a cation exchange resin.
A different strategy is to synthesize soluble, oxide-supported organometallic catalyst precursors which could then be characterized and studied by employing a wide range of solution spectroscopic and kinetic methods. The present invention represents the first such examples of organic solvent soluble, atomically dispersed, oxide-supported catalyst precursors, covalently bonded iridium-heteropolyanions.
It is therefore an object of this invention to provide novel compounds wherein a covalent iridium-polyoxoanion bond remains stable under the conditions of catalytic hydrogenation.
It is a further object of this invention to provide catalyst systems which avoid Ir(1) formation under hydrogenation reaction conditions.
It is a further object of this invention to provide a catalyst system which can be readily and economically separated from the hydrogenation reaction mass by binding to an anion exchange resin.
It is a still further object of this invention to provide a catalyst system which is similar in chemical reactivity to atomically dispersed oxide-supported iridium complexes (e.g., Ir/Al2 O3) while being homogeneous and soluble.
It is still a further object of the present invention to provide a covalently bonded Ir.polyoxoanion system which will support the metal on the polyoxoanion in a Cl- and PPh3 -free system.
It is yet another object of the invention to provide a covalently bonded Ir.polyoxoanion system which will impede Ir(0) formation in a Cl- and PPh3 -free system.
It is yet another object of the invention to
provide a covalently bonded Ir.polyoxoanion system which will prevent attachment of Ir(1) to a cation exchange resin.
These and further objects of the invention will become apparent to those skilled in the art with reference to the description below.
The present invention provides novel liquid-phase olefin hydrogenation catalyst precursors which comprise either Dawson or Keggin structures represented in their ionic form by [Ln Ir(1).X2 M15 M'3 O62 ]x- and [Ln Ir(1).XM9 M'3 O40 ]y-, respectively. L represents a ligand chosen from 1,5-cyclooctadiene (COD), ethylene, cyclooctene, norbornadiene and other olefinic ligands; n=1 or 2 depending upon the number of double bonds present in the ligand L. X is the "hetero" atom chosen from B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu. M is either W or Mo. M' is preferably Nb or V, but Ti, Zr, Ta, Hf are also useful. Preferred species of the novel compounds comprise X+ 8[Ln Ir..P2 W15 Nb3 O62 ]-8 and Y+6 [Ln Ir.SiW9 Nb3 O40 ]-6. The first preferred species is prepared by reacting under nitrogen (Bu4 N)9 P2 W15 Nb3 O62 with [Ir(COD)(CH3 CN)2 ]BF4 in the presence of acetonitrile to obtain (Bu4 N)8 [(COD)Ir.P2 W15 Nb3 O62 ] and Bu4 NBF4, and treating (Bu4 N)8 [(COD)Ir.P2 W15 Nb3 O62 ] with acetone at 40 psig H2 at 25° C. for less than one hour to obtain the activated catalyst complex (Bu4 N)8 [L'n Ir.P2 W15 Nb3 O62 ] and cyclooctane. The second preferred species is prepared by reacting (Bu4 N)7 SiW9 Nb3 O40 with [Ir(COD)(CH3 CN)2 ]BF4 in the presence of acetonitrile to obtain (Bu4 N)6 [(COD)Ir.SiW9 Nb3 O40 ] and Bu4 NBF4, and treating (Bu4 N)6 [(COD)Ir.SiW9 Nb3 O40 ] with acetone at 40 psig H2 at 25°C for one-half hour to obtain the activated catalyst complex (Bu4 N)6 [L'n Ir.SiW9 Nb3 O40 ] and cyclooctane.
FIG. 1 comprises plots of the pressure of hydrogen versus time during cyclohexene hydrogenation.
FIG. 2 is a plot of initial rate of catalytic hydrogenation of cyclohexene as a function of the ratio
of Ir:SiW9 Nb3 O407-.
FIG. 3 is a plot of a spectrophotometric titration of a) SiW9 Nb3 O407- and b) P2 W15 Nb3 O62 9- with Ir(COD)+ under 40 psig CO.
In aqueous solutions certain metal oxides undergo stepwise hydrolysis-oligomerization reactions upon acidification according to the following representative stoichiometries ["Heteropoly and Isopoly Oxometalates" by M. T. Pope (Springer-Verlag, N.Y., 1983)]:
2aH+ +bMOn-r →[Mb Oy ]-p +aH2 O(1)
where
bn=y +a (oxygen atom balance)
br-2a=p (charge balance)
2aH+ +bMOn-r +cXOq-s →[Xc Mb Oy ]-p +aH2 O (2)
where
bn+cq=y+a (oxygen atom balance)
br+cs-2a=p (charge balance) and where M can be one of several metals, e.g., W, Mo, V, or mixtures of these metals. X is usually P or Si but can be a number of other elements. The condensed metal oxides, e.g., [Xc Mb Oy ]-p, form a symmetric three dimensional array whose structure, composition, and properties can vary a great deal with various X's and M's. Which structure is present depends on the acidity of the solution, the initial amounts of MOn -r and XOq-s, and other reaction conditions. In some cases, even under the same reaction conditions, different structures may be present. Products formed by reaction (1) are called isopolyoxoanions. Products formed by reaction (2) contain a "hetero" atom X, usually centrally located in the structure, and as a result theses products are referred to as heteropolyoxoanions.
Catalysis via polyoxoanion supported (covalently bonded) transition metals has heretofore gone largely unrecognized despite the potential such compounds represent in terms of a new class of atomically dispersed oxide-supported catalysts. It is important here to appreciate the distinction between transition metals supported on a polyoxoanion, as opposed to a metal incorporated into a polyoxoanion. By polyoxoanion supported metals we mean species that are firmly attached to a K3-O site of surface oxygens of a polyoxoanion analogous to the envisioned situation of at least some-oxide supported heterogeneous catalysts. This situation is quite different from the more common one of metals or organometallics incorporated into a vacancy in the polyoxoanion framework by four, approximately square-planar oxide ligands, e.g., CpTi+3 incorporated into PW11O 397- or Mo5 O186- as PW11 O39 (CpTi)4- and Mo5 O18 (CpTi)3-, respectively, or the incorporated Nb+5 in NbW5 O19 3-, Nb2 W4 O19 4-, or SiW9 Nb3 O407-. Metals supported on a polyoxoanion surface (but not incorporated metals) can have cis-coordination sites, greater coordinative unsaturation, and perhaps mobility on the oxide surface, all leading to reactions and mechanisms unavailable to incorporated metals and thus to distinctive catalytic chemistries. Also worth distinguishing here are organometallics bound by a single, labile bridging oxygen, cases where the polyoxoanion behaves like a simple alkoxide, RO--, e.g., RO--U(Cp)3 --OR (OR=--OMW5 O193- ; M=Ta5+, Nb5+)3 rather than as a tight binding, K3 --O ligand or support.
Two key experimental tests of a tightly and covalently polyoxoanion supported metal cation are: 1) whether the metal will be reduced to M(0) under H2 ; and 2) whether a cation exchange resin will remove the metal from contact with the polyoxoanion. By these tests the Ir(1).[SiW9 Nb3 O40 ]7- or P2 W15 Nb3 O629- ] disclosed herein is covalently bonded, while RhCl(PPh3)3 +SiW12 O404- or SiMo12 O404- is clearly not covalently bonded.
For purposes of brevity in the specification, the first novel preferred species of the present invention, X+8[L'n Ir.P2 W15 Nb3 O62 ]-8 will hereinafter be referred to as the iridium mixed phosphotungstate complex. The second preferred species, Y+6 [L'n Ir.SiW9 Nb3 O40 ]-6, will be hereinafter referred to as the iridium mixed silicotungstate complex.
The novel compounds which constitute the present invention are polyoxoanion supported metal complexes. At the time of filing this application, only the composition of the catalyst precursor is reasonably well characterized. The actual species which are present in situ during olefin hydrogenation has not been precisely determined.
As is well known in the art, heteropolyanions can be characterized as either Dawson or Keggin structures. The first genus of the precursors of the present invention is a Dawson structure polyoxoanion represented by the following formula:
[Ln Ir.(1).X2 M15 M'3 O62 ]x-(3)
The second genus is represented by the Keggin structure whose formula is as follows:
[Ln Ir.(1).XM9 M'3 O40 ]y-, (4)
For each of these formula, L is an olefinic ligand, preferably chosen from the group consisting of 1,5-cyclooctadiene (COD), cyclooctene, norbornodiene and ethylene; n is 1 or 2, depending upon the number of available electron pairs within the ligand. X is the "hetero" atom chosen from the group consisting of B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu. M is W or Mo. M' is preferably Nb or V, but may also be chosen from the group consisting of Ti, Zr, Ta or Hf. The ionic charge of the composition, x and y, is easily calculated by one of ordinary skill in the art, once the various atoms in the molecule are known.
The countercation for the polyoxoanion supported metal complex is chosen from two broad categories of cations. One preferred countercation is tetrabutyl ammonium. The second group of countercations consists of alkali metals chosen from the group consisting of Na+, K+, Rb+, and Cs+. Other cations are possible, including di- or higher valency cations.
The novel compositions of the instant invention have demonstrated specific utility in the catalytic hydrogenation of olefins in the liquid phase.
(Bu4 N)7 SiW9 Nb3 O40 is described in Finke, R. G.; Droge, M. W.; J. Am. Chem. Soc.. 1984, 106, 7274.
K7 HNb6 O19.H2 O
This isopolyniobate was obtained in a modification of literature procedures by fusing 10 g Nb2 O5 in about 20 g solid KOH by heating with a bunsen burner in a nickel crucible until a molten liquid formed. After cooling, the solid was broken out of the crucible, carefully dissolved in about 200 ml distilled H2 O, and filtered to remove some fine, insoluble material. The product was precipitated with an equal volume of 95% enthanol and vigorous hand stirring using a glass rod. The white solid which formed was collected and washed with 95% ethanol. The solid was redissolved in H2 O, reprecipitated with 95% ethanol, and collected twice more. After drying at 60°C, the yield was 16 g (94%).
A-β-Na9 HSiW9 O34.23 H2 O
This trivacant heteropolytungstate was prepared by a modified literature procedure. 60 g of Na2 SiO3.9 H2 O was dissolved in 400 ml distilled H2 O. 362 g of Na2 WO4.2H2 O was then added and the solution was stirred until homogeneous. 200 ml 6M HCl was slowly added to the vigorously stirring solution. The gelatinous precipitate which formed during acid addition was removed by filtration and the clear filtrate was allowed to crystallize at 5°C for several days. Following collection and air drying, variable yields of the white crystalline solid were obtained (50-80 g, 14 to 23%).
[Bu4 N]6 H2 Si2 W18 Nb6 O77
24.0 g of K7 HNb6 O19.13 H2 O (17.5 mmole) was dissolved in 3L of a 0.5M H2 O2 solution. Addition of 41 ml 6 M HCl (246 mmole) turned the pale yellow solution to bright yellow. 100.0 g A-β-Na9 HSiW9 O3.23 H2 O (35.1 mmole) was added to the stirring yellow solution resulting in gas evolution and a color change from yellow to orange. After the SiW9 O3410- dissolved, all peroxides were destroyed by the careful addition of 200.Og NaHSO3 (1922 mmoles, excess). (CAUTION! Do the previous step in a well-ventilated hood.) The solution became colorless and was vigorously stirred for 2 hours. The product was precipitated as the tetra-n-butylammonium (Bu4 N+) salt by the addition of 50.0 g solid Bu4 NBr (155 mmoles). The product was collected, washed with distilled water (0.75-1 L), 95% ethanol (0.75-1 L), diethyl ether (0.75-1 L), and dried overnight at 60°C
The solid was then dissolved in 700 ml boiling CH3 CN. The cloudy solution was filtered hot through a pad of Celite Analytical Filter Aid. (Any cloudiness that persisted or formed after filtration was removed by the following acidification step.) 6 M HCl was added in small portions (5-10 ml) to the stirring CH3 CN solution. Any remaining cloudiness was immediately removed on initial acid addition and a clear solution resulted. After about 200 ml of added acid, the solution became cloudy. The stirring rate was increased and a white crystalline solid separates. An additional 100 ml of the acid was added to ensure complete precipitation. The product was collected, washed with distilled water and dried under aspiration. This was followed by washings with 95% ethanol and diethyl ether, largely to dry the material on the frit and facilitate further manipulations. Both the filtrate and the washings were saved, combined and reduced in volume to recover any uncollected product. The products were combined and dried at 60°C to a constant weight of 112 g (Bu4 N)6 H2 Si2 W18 Nb6 O77 (97%) obtained as a white powder in two to three crops.
The product was dissolved in 1 L boiling CH3 CN by reducing the solution volume to about 400 ml and cooling at 5°C overnight. The product was collected, washed with cold CH3 CN, and dried at 60°C Recovery was 81 g in two crops, for a 72% recovery and a 70% overall yield (116 g expected). Analysis Calculated for [C96H218 N6 Si2 W18 Nb6 O77 ]: C, 17.44; H, 3.32; N, 1.27; Si, 0.85; W, 50.05; Nb, 8,43. Found: C, 17.40; H, 3.41; N, 1.33; Si, 0.85; W, 50.50; Nb, 8.15.
The [(n-C4 H9)4 N]7 HSi2 W18 Nb6 O77 salt was obtained by crystallization of the crude product (before acidification) from a concentrated CH3 CN solution. Isolated yields were typically 30-50%. Ana. Calcd for [C112 H253 N7 ]: C, 19.63; H, 3.71; N, 1.43. Found: C, 19.66; H, 3.74; N. 1.44. The anion can be reliably identified by its characteristic 183 W NMR spectrum.
The 183 W NMR sample was prepared by dissolving 2.0 g of (Bu4 N)6 H2 Si2 W18 Nb6 O77 with 3 ml CD3 CN followed by addition of base (i.e., alkylamine, pyridine, water).
All IR spectra were recorded referenced to the CD2 HCN solvent.
(Bu4 N)6 H2 Si2 W18 Nb6 O77 (0.250 g) was dissolved in 10.0 ml CH3 CN. First, eight equivalents of tri-n-butylamine (0.072 ml) was added by syringe and the solution was refluxed for 30 minutes. After cooling, a small aliquot was used to record the infrared absorption spectrum (no change in 690 cm-1 band) Next, 72 equivalents tri-b-butylamine (0.648 ml; for a total of 80 eq) was added with the reflux and IR steps
35 repeated (no change in 690 cm-1 band). Finally, 80 equivalents H2 O (0.040 ml) was added repeating the reflux and IR steps (80% loss of 690 cm-1 band).
(Bu4 N)6 H2 Si2 W18 Nb6 O77 (0.250 g) was dissolved in 10.0 ml CH3 CN. Eight equivalents n-butylamine (0.030 ml) was added by syringe and the solution was refluxed for 30 minutes. A small aliquot was used to record the infrared absorption spectrum (50% loss of 690 cm-1 band). An additional 6 equivalents of n-butylamine (0.022 ml; for a total of 14 eq) was added and the solution was allowed to stand overnight at the ambient glove box temperature (25°-30°C). The infrared spectrum was then recorded (complete loss of 690 cm-1 band)
[(n-C4 H9)4 N]7 SiW9 Nb3 O40
In a typical reaction, 1.5000 g of (Bu4 N)6 H2 Si2 W18 Nb6 O77 (0.23 mmole) was dissolved in about 20 ml CH3 CN. 8.0 equivalents of a [(n-C4 H9)4 NOH]solution (40% in water) which had been previously titrated with standard HCl to a methyl red endpoint was added by syringe. In this case, 1.11 ml (1.81 mmole) of 40% Bu4 NOH/H2 O at 1.63 M were required. The solvent was removed by rotary evaporation at 80°C under vacuum for 2-3 hours.
Na12 P2 W15 O56.19 H2 O
Na12 P2 W15 O56.H2 O (previously formulated as "Na12 P2 W16 O58 ") was prepared according to the following slightly modified literature procedure. Sodium perchlorate (107 g) was added to an aqueous solution of pure α-K6 P2 W8 O62.15 H2 O (75 g in 250 ml water) and was stirred for 2 hrs. The insoluble KClO4 was removed by filtration and 1 M Na2 CO3 was added to reach pH 9 (roughly 200 ml) which was maintained by base addition as required for 1 hr. with constant stirring The original light yellow solution turned colorless and then a white precipitate was formed which was collected on a coarse frit and washed with successive portions of 75 ml saturated NaCl solution, 75 ml 95% ethanol, and 75 ml diethyl ether. The product was then dried overnight at 60°C TGA (thermal gravimetric analysis) indicated 19 waters of hydration. Yield: 60 g (83%). Drying can also be accomplished by a dessicator over concentrated H2 SO4 for two days to yield a .18 H2 O hydrate (by TGA). Drying over concentrated H2 SO4 for longer periods of time results in a hydroscopic product. (Note that a report of crystalline Na12 P2 W15 O56.x H2 O has not appeared and the present literature synthesis probably produces impure material. Purification via recrystallization is possible at the next step, however, vide infra.).
(Me4N)12 H4 P4 W30 Nb6 O123.16 H2 O
A pale yellow solution of 2.95 g K7 HNb6 O19.19 H2 O (2.15 mmole) dissolved in 325 ml 0.5 H2 O2 was prepared. Next, 29 ml of 1 M HCl was added followed by 18.25 g Na12 P2 W15 O56.19 H2 O (4.22 mmole). Aft®r complete dissolution of the Na12 P2 W15 O56, NaHSO3 (25 g) was added resulting in a clear, colorless solution. The resulting solution was stirred 5 minutes before addition of a large excess (≈10 g) of tetramethylammonium chloride. The white precipitate was collected, recrystallized twice from hot, unbuffered, pH 4.6 water and dried under vacuum (0.1-0.3 torr) overnight at 25°C Yield: 15.4 g (75%). Several TGA's done on samples prepared throughout the course of these studies show an average of 16±6 waters of hydration. Analysis for C48 H148 N 12 P4 W30 Nb6 O123.16 H2 O; Calc: C, 6.15%; H, 1.61%; N, 1.79%; P, 1.32%; Nb, 5.95%; W, 58.90%. Found: C, 6.65%; H, 1.97%; N, 1.86%; P, 1.03%; Nb, 5.67%; W, 59.29%; K, 0%; Na, 0%.
This procedure has been successfully completed more than a dozen times by as many as four different people with satisfactory results each time.
(Bu4 N)12 H4 P4 W30 Nb6 O123
(Me4 N)12 H4 P4 W30 Nb6 O123.16 H2 O (15 g, 1.60 mmole) was dissolved in hot, pH 4.6 water (500 ml) and filtered over Celite Analytical Filter Aid (when necessary) to obtain a clear solution. The solution was then allowed to cool to room temperature. Addition of aqueous tetrabutylammonium bromide (7 g in 20 ml water) resulted in a rise in pH to 5.8 along with the formation of a white precipitate of the product. The precipitate was collected, washed well with water (to remove excess tetrabutylammonium bromide) and dried at 60°C for 12 hrs. to yield 17.7 g (100%). Material dried in this fashion generally showed ≦0.5 H2 O by TGA, consistent with the general findings of others. Analysis for the dimer C192 H436 N12 P4 W30 Nb6 O123 : Calc.: C, 20.78%; H, 3.98%; N, 1.51%; P, 1.12%; Nb, 5.02%; W, 49.71%. Found (analysis by Galbriath Laboratories): C, 20.50%; H, 3.95%; N, 1.50%; P. 0.99%; Nb, 5.16%; W, 49.96%.
Attempts to recrystallize this product were unsuccessful and reprecipitation from a saturated acetone solution to which a few drops of neutral water had been added, followed by cooling at 5°C for a few days, provided a fine powder. After drying at 60°C for 12 hrs. this powder was found to be less pure by elemental analysis than the original material. Analysis for the dimer C192 H436 N12 P4 W30 Nb6 O123 : Calc.: C, 20.78%; H, 3.98%; N, 1.51%; P, 1.12%; Nb, 5.02%; W, 49.71%. Found: C, 19.84%; H, 3.91%; N, I.50%; P, 1.13%; Nb, 4.66%; W, 50.03%.
Recrystallization/reprecipitation was also attempted from acetone/pH 2 water but this yielded decomposition to P2 W18 O626- (31 P NMR in CH3 CN; δ=-12.7, α isomer, and δ=-11.0 and -11.6, β isomer). Minimizing the number of manipulations gave the best, analytically pure material, so that the initial, well-washed and dried product was chosen for subsequent experiments.
(Bu4 N)9 P2 W15 Nb3 O62
A 3.00 g sample of the dimer (Bu4 N)12 H4 P4 W30 Nb6 O123 (0.271 mmole) was dissolved in 10 ml acetonitrile. To this solution was added 3.0 equivalents per monomer (1.03 ml) of aqueous Bu4 NOH (40% by weight, 1.57 molar) and stirred at room temperature for 0.5 hrs. Solid (Bu4 N)9 P2 W15 Nb3 O62 was obtained by removal of the solvent under vacuum at 25°C for 24 hrs. We have been unable to crystallize (Bu4 N)9 P2 W15 Nb3 O62 to date, presumably due to the inability of the preferred lattice to accommodate more than six Bu4 N+ cations. However, a crystalline product can be obtained if the DBU.H+ (DBU=1,8-diazabicyclo[5.4∅]undec-7-ene) salt is prepared as described below. Purity of the non-crystalline (Bu4 N)9 P2 W15 Nb3 O62 was ascertained by 31 P NMR. All (Bu4 N)9 P2 W15 Nb3 O62 used in this work exhibited a 31 P NMR consisting predominantly of the anticipated two lines (δ=-7.3 and -14.1±0.2 ppm) and two less intense signals at δ=-9.1 and -13.8±0.2 ppm (both of <5% relative intensity). These latter two lines are not present in material that has been placed in a 60°C oven for 24 hrs. TGA failed to show any solvates in material dried either under vacuum or at 60°C for 24 hrs.
Experience has shown that (Bu4 N)9 P2 W15 Nb3 O62 has a short shelf life. Therefore, it is suggested that this material be prepared as needed and prolonged storage (greater than two weeks) be avoided.
(DBU.19 H)9 P2 W15 Nb3 O62.11 H2 O
To a warm (≈30°C) aqueous solution of 5.0 g (0.535 mmole) (Me4 N)12 H4 P4 W30 Nb6 O123.16 H2 O was added, with stirring an excess (2.00 g, 10.6 mmole) of DBU.HCl. Cooling to 0°C overnight yielded a white precipitate which was collected, washed with 95% ethanol, then dried at 80°C under 0.1-0.3 torr for 3 hrs., to yield 5.2 g. Three grams of this material were then slurried in 100 ml of refluxing CH3 CN/DMSO (5:1) and about 1.5 ml DBU was added. Refluxing was continued for 17 hrs., after which time the solution had become homogeneous. The volume of the solution was condensed to 25 ml and addition of 95% ethanol resulted in precipitation of the crude product as a white powder. Crystallization was accomplished by slowly cooling a hot, saturated CH3 CN/H2 O (1:1, v/v) solution at 5° C. overnight. Drying at room temperature under 0.1-0.3 torr for 3 hrs. resulted in 2.50 g (0.441 mmole), 41%. TGA was consistent with 11 waters of hydration. Analysis for C81 H175 N18 P2 W15 Nb3 O73 ; Cal.: C, 17.17%; H, 3.I1%; N, 4.45%; P, 1.09%; Nb, 4.92%; W, 48.66%. Found: C, 16.76%; H, 3.15%; N, 4.47%; P, 1.01%; Nb, 4.45%; W, 49.49%.
Instrumentation/Analytical Procedures. 31 P NMR spectra (I46.18 MHz) were recorded on a Nicolet NT-360 spectrometer using 12 mm o.d. sample tubes and referenced, by the substitution method, to 1% H3 PO4 in D2 O. Chemical shifts are reported in parts per million with negative values upfield of the standard.
Preparation of [Ir(COD)Cl]2.
This compound is prepared by the literature methods from either IrC13.3 H2 O or (NH4)2 IrCl6. See Herde, J. L.; Lambert, J. C.; Senoff, C. V., Inorg. Syn.. 1974, 15, 18; Crabtree, R. H.; Quirk, J. M; Felkin, H.; Fillebeen-Kahn, T.; Synth. React. Inorg. Met.--Org. Chem. 1982, 12, 407. Generally this synthesis is done on a 0.5-1.0 g scale to yield 70-91% of red to red-brown [Ir(COD)Cl]2. Purity is ascertained by 1 H NMR. Occasionally, a batch of IrCl3.3 H2 O is encountered which gives low (<40%) yield of [Ir(COD)Cl]2. This problem can be a avoided by using (NH4)2 IrCl6. The [Ir(COD)Cl]2 compound is known to be O2 sensitive (Alhay, M. H. et al., Can. J. Chem. 61:1332 (1983)) so that its exposure to air should be avoided.
Synthesis of [Ir(COD)(CH3 CN)2 ]BF4.
This modified literature synthesis (Green, M.: J. Chem. Soc., (A) 1971, 2334) is best done under a nitrogen atmosphere but can be successfully accomplished under air if solutions containing the solvate are vigorously purged with nitrogen and exposure to air (oxygen) kept to an absolute minimum. A typical preparation is as follows: To 10 ml of acetonitrile (degassed by purging with N2 for 15 min) was added 0.10643 g (0.159 mmol) [Ir(COD)Cl]2. To this mixture was added 0.06270 g (0.322 mmol, 2.0 equivalents) AgBF4 and the mixture stirred for 30 min. The white AgCl precipitate was removed by filtration over Celite to yield a clear yellow to yellow/orange filtrate Best results are obtained when the filtrate is used directly rather than isolating the [Ir(COD)(CH3 CN)2 ]BF4 product, however a yellow precipitate of [Ir(COD)(CH3 CN)2 ]BF4 can be obtained by slowly adding the acetonitrile solution to diethyl ether (although oiling is occasionally a problem). Filtration over a medium frit is followed by washing with Et2 O and drying under high vacuum at room temperature for 12-18 h. Purity of the solvate was determined by 1 H NMR. The corresponding NO3-, PF6-, and ClO4- salts are similarly prepared from [Ir(COD)Cl]2 and the appropriate silver salt.
The Iridium Mixed Silicotungstate Complex: (Bu4 N)6 [(COD)Ir.SiW9 Nb3 O40 ].Bu4 NBF4.6 H2 O∅5CH3 CN.
This synthesis is best performed under an N2 atmosphere, but can be successfully accomplished under air if solutions containing [Ir(COD)(CH3 CN)2 ]+ are vigorously purged with N2 and exposure to air is minimized. An acetonitrile solution of 1-2 g of (Bu4 N)7 SiW9 Nb3 O40 (see Example 1) is added to a nitrogen purged, acetonitrile solution of 1 eq [Ir(COD)(CH3 CN)2 ]BF4 (this synthesis works equally well when [Ir(COD)(CH3 CN)3 ]+ X-, X- =NO3-, PF6-, or ClO4-, is used instead of [Ir(COD)(CH3 CN)2 ]BF4) followed by removal of the solvents under vacuum. The product is amorphous and all attempts to recrystallize it have failed due to the large number of Bu4 N+ cations (Finke, R. G.; Rapko, B.; Saxton, R. J.; Domaille, P. J.; J. Am. Chem. Soc.. 1986, 108, 2947). Consequently, the iridium mixed silicotungstate complex contains 1 eq of Bu4 NBF4. Control experiments in which a large excess (400 eq) of Bu4 NBF4 were added to the iridium mixed silicotungstate complex indicate that this byproduct has no effect on the rate of cyclohexene hydrogenation catalyzed by the iridium mixed silicotungstate complex.
The number of solvates, determined by TGA, is consistent with 6 H2 O and 0.5 CH3 CN: calculated 2.67% solvent loss for 6 H2 O and 0.5 CH3 CN; found 2.55% weight loss. The presence of 0.5±0.35 eq CH3 CN was confirmed by GLC. Elemental analysis of the iridium mixed silicotungstate complex: calculated values for the 6H2 O, 0.5 CH3 CN solvate C121 H277.5N7.5IrSiW9 Nb3 O46.BF4 : C, 30.18; H, 5.81; N, 2.18; W, 34.37; lr, 3.99; Si, 0.59%; Nb, 5.79. Found: C, 30.07%; H, 5.70; N, 2.54; W, 34.40; Ir, 4.38; Si, 0.93; Nb, 6.61.
The IR spectrum (CH3 CN) of the iridium mixed silicotungstate complex shows the characteristic absorbances of a Keggin type heteropolyanion: 1104 (w), 994 (m), 952 (m), 888 (s), 804 (s), 784 (s, sh).
The intratriad M-0-M stretching band (nominally 800 cm- is split (804 and 784 cm-1) indicating a bonding interaction between iridium and the polyoxoanion. This splitting phenomenon has been documented for many polyoxoanion-supported organometallic complexes. See, e.g., Finke, R. G.; Rapko, B; Domaille, P. J.; Organometallics 1986, 5, 175.
The presence of 1.0 eq COD was confirmed by detection of 1.0±0.1 eg cyclooctane (by glc) after reaction of the iridium mixed silicotungstate complex with hydrogen. 1 H and 13 C NMR of a 0.02 M solution of the iridium mixed silicotungstate complex in either d6 -Me2 SO or CD3CN failed to reveal the expected resonances which could be attributed to coordinated or free COD.
An Alternate Preparation of the Precatalyst [(Bu4 N)6 (COD)Ir.SiW9 Nb3 O40 ].Bu4 NClO4,1.
Into an 18×120 mm t®st tube is placed 89.68 mg (0.133 mmol) [Ir(COD)Cl]2 and 50.16 mg (0.242 mmol)--not quite 2.0 equivalents to avoid the presence of Ag+ in the product--AgClO4. Fifteen ml degassed (by N2 purge for 15 min) CH3 CN is added, followed by a N2 purge for 30 min. After this time the yellow solution is filtered through Celite to remove the AgCl ppt. The Celite pad is washed three 1 ml portions of degassed (by N2 purge) CH3 CN. A separate solution of 1.04 mg (0.242 mmol) (Bu4 N)7 SiW9 Nb3 O40 in 10 ml CH3 CN and 5 ml H2 O (which had been previously prepared and purged for 15 min with N2) is drawn through the Celite pad and into the yellow filtrate containing [Ir(COD)(CH3 CN)2 ]ClO4 while continually stirring the solution to ensure adequate mixing. The Celite pad is again washed with three portions of CH3 CN (about 5 ml total, does not have to be degassed) and then the combined filtrate and washings are placed in a 50 ml round bottom flask and reduced in volume (by rotovaporation) to about 8 ml. At this point the solvent present is mostly water; the orange-brown [(Bu4 N)6 (COD)Ir.SiW9 Nb3 O40 ] oils out and foaming becomes a problem. The flask and contents are removed from the rotovaporator and 25 ml, 1,2-dichloroethane is added. The orange-brown oil readily dissolves in the 1,2-dichloroethane. The layers are separated and the aqueous fraction discarded while the 1,2-dichloroethane is removed under vacuum (0.1-0.3 torr, room temperature) to yield the product as an amorphous orange-brown solid.
It was hoped that the Bu4 NClO4 would not be extracted into the 1,2-dichloroethane, but this proved not to be true. Attempted fractional precipitation of Bu4 NC104 from CH3 CN/H2 O, EtOH/CH3 CN, and CHCl3 /CH3 CN solvent mixtures also failed to yield the desired separation.
The sample is dried under high vacuum (0.1 torr) at 80°C for 12 h. Dried in this manner, the product is hygroscopic.
No solvates are detected by TGA. Elemental analysis of 1: calculated for C120 H264 N7 IrSiW9 Nb3 O40.ClO4 : C., 30.66; H, 5.66; N, 2.09; W, 35.21; Nb, 5.93; Ir, 4.09; Si, 0.60. Found: C, 30.31; H, 5.59; N, 2.10; W, 35.35; Nb, 5.83; Ir, 4.16; Si, 0.76.
The Iridium Mixed Phosphotungstate Complex: (Bu4 N)8 [(COD)Ir.P2 WI5Nb3 O62 ].Bu4 NBF4.9 H2 O.
Typically, a degassed acetonitrile solution of 1-2 g (Bu4 N)9 P2 W15 Nb3 O62 is added to a degassed acetonitrile solution of 1 eq [Ir(COD)(CH3 CN)2 ]BF4 (see Example 4 above) followed by removal of the solvents under vacuum to yield an amorphous solid. The yield is quantitative and attempts to recrystallize the iridium mixed phosphotungstate complex have failed. Thus, the iridium mixed phosphotungstate complex contains 1 eq of Bu4 NBF4. However, it was determined that this impurity has no effect on the rate of catalytic hydrogenations since addition of 400 eq Bu4 NBF4 to the iridium mixed phosphotungstate complex as well as Bu4 NBF4 -free iridium mixed phosphotungstate complex (See Example 8, prepared from [Ir(COD)(CH3 CN)2 ]ClO4 and removal of the insoluble Bu4 NClO4) yield experimentally similar hydrogenation rates. No CH3 CN was detected by GLC. The number of solvates, determined by TGA, is consistent with 9 H2 O: calculated 2.38% weight loss for 9 H2 O; found 2.40% weight loss. Elemental analysis of the iridium mixed phosphotungstate complex: calculated for the 9 H2 O solvate C152 H354 N9 IrP2 W15 Nb3 O71.BF4 : C, 26.76; H, 5.23; N, 1.85; W, 40.43; Nb, 4.09; Ir, 2.82; P, 0.91. Found: C, 26.52; H, 4.95; N, 2.13; W, 40.82; Nb, 3.98; Ir, 2.97; P, 0.69.
The IR spectrum (CH3 CN) of the iridium mixed phosphotungstate complex is typical of a Dawson type heteropolyanion: 1096 (w), 994 (m), 895 (m), 809 (s), 783 (s, sh). The intratriad M-O-M stretching band (nominally 800 cm-1 is split (809 and 783 cm-1) indicating a bonding interaction between iridium and the polyoxoanion. This splitting phenomenon has been documented for many polyoxoanion-supported organometallic complexes.
The presence of 1.0 eq COD was confirmed by detection of 1.0 eq cyclooctane (by GLC) after reaction of the iridium mixed phosphotungstate complex with hydrogen. Displacement of the coordinated COD in the iridium mixed phosphotungstate complex by excess NBD (free COD measured by 1 H NMR) confirmed this result even though coordinated COD could not be detected by either 1 H or 13 C NMR of a 0.02 M CD3 CN solution of the iridium mixed phosphotungstate complex.
[Bu4 N)8 (COD)Ir.P2 W15 Nb3 O62 ]n, 2.
Into 10 ml of acetonitrile is added 106.53 mg (0.158 mmol) [Ir(COD)Cl]2 and the mixture degassed by application of a N2 purge for 15 min. To this slurry is added 68.06 mg (0.328 mmol) AgClO4. A white precipitate forms immediately and the solution color changes from orange to yellow. The N2 purge is continued for another 15 min. After this time, the yellow solution is filtered through Celite to remove the AgCl ppt. The Celite pad is washed three 1 ml portions of degassed (by N2 purge) CH3 CN. A separate solution of 505.29 mg (0.080 mmol) (BU4N)9 P2 W15 Nb3 O62 in 10 ml CH3 CN and 5 ml H2 O (which had been previously prepared and purged for 5 min with N2) is drawn through the Celite pad and into the yellow filtrate containing [Ir(COD)(CH3 CN)ClO4 while continually stirring the solution to ensure adequate mixing. During this addition the color of the solution changes from yellow to amber. The Celite pad is again washed with three portions of CH3 CN (about 5 ml total, does not have to be degassed) and then the combined filtrate and washings are placed in a 50 ml round bottom flask and reduced in volume (by rotovaporation) to about 5 ml. Three ml of a 1:1 EtOH/H2 O solution is added, followed by cooling to 0°C, resulting in a small amount of white precipitate which is separated from the amber mother liquor by centrifugation or filtration through Celite. The mother liquor is rotovapped to dryness, then dried at 80°C under high vacuum (0.1 torr) for 12 hrs. Dried in this fashion, the product is hygroscopic.
The extraction procedure described above for separation of Bu4 NClO4 from 1 does not work well in this case (an emulsion readily forms). No solvates are detected by TGA. Elemental analysis of 2: calculated for C136 H300 N5 IrP2 W15 Nb3 O62 :°C, 25.80; H, 4.78; N, 1.77; W, 43.56; Nb, 4.40; Ir, 3.04; P, 0.98. Found: C, 25.85; H, 5.04; N, 1.95; W, 43.35; Nb, 4.20; lr, 2.71; p, 0.63.
Synthesis of [IrH2 (acetone)2 (PPh3)2 ]BF4.
This catalyst is prepared (Crabtree, R. H.; Mellea, M. F.; Mihelcic, J. M.; Quirk, J. M., J. Am. Chem. Soc..1982, 104, 107) by the action of hydrogen on a cold, acetone solution of [Ir(COD)(PPh3)2 ]PF6. (Haines, L. M.; Singleton, E., J. Chem. Soc., Dalton Trans. 1972, 1891.) Since the reduction of coordinated COD occurs almost immediately, identical hydrogenation activity is obtained by using the precursor directly. This compound is synthesized and used herein to enable comparison of the catalytic hydrogenation activity of the claimed novel compounds versus the well characterized Crabtree's catalyst.
(Ir(0))n, Precipitated Iridium(0)).
An acetone solution of either [Ir(COD)(CH3 CN)2 ]BF4 or the iridium mixed silicotungstate complex (0.001-0.01M) is placed under 40 psig H2 with rapid stirring. At room temperature (≈22° C.) the reduction of [Ir(COD)(CH3 CN)2 ]+ occurs immediately, while reduction of the iridium mixed silicotungstate complex occurs more slowly, requiring>0.5 h to go to completion. For this reason, reductions of the iridium mixed silicotungstate to are allowed to proceed under 40 psig H2 for 2-3 h. The (IR(0))n was either used in situ or collected by centrifugation followed by washing with acetone 3 times before drying under high vacuum at room temperature for 18 hours. Yields were 83% and 73% for, respectively, (Ir(0))n obtained from [Ir(COD)(CH3 CN)2 ]BF4 and the iridium mixed silicotungstate complex. In the case of (Ir(0))n prepared from the iridium mixed silicotungstate complex, the mother liquor is black yet transparent to light. However, the black solution was tested for catalytic hydrogenation activity and found to be completely inactive. These results indicate that, under these conditions, the iridium colloid that forms is unlikely to be catalytically active. Evaporation of the solvent yields a brown-black product which analyzes for 79% Ir.
Synthesis of the Carbonyl Iridium Mixed Silicotungstate Complex [(OC)2 Ir.SiW9 Nb3 O40 ]6-, and the Carbonyl Iridium Mixed Phosphotungstate Complex [(OC)2 Ir.P2 W15 Nb3 O62 ]8-.
These complexes are prepared at room temperature by subjecting an acetone solution of either the iridium mixed silicotungstate complex or the iridium mixed phosphotungstate complex to 40 psig CO for 15-30 min. The IR spectrum of the carbonyl iridium mixed silicotungstate complex shows two strong absorbances (νCO =2050 cm-1 and 1975 cm-1). Similarly, the IR spectrum of the carbonyl iridium mixed phosphotungstate also exhibits two absorbances (μCO =2060 cm-1 and 1980 cm-1). The assignment of these IR bands of carbonyl vibrations was confirmed by the shift to lower energy when 13CO was used to prepare both dicarbonyls (νCO=2000 cm-1, 1930 cm-1 and 2015 cm-1, 1935 cm-1, respectively). In comparison, [Ir(CO)2 (CH3 CN)2 ]BF4 (prepared by treating a 3 ml acetone solution containing 200 mg [Ir(COD)(CH3 CN)2 ]BF4 with 40 psig CO for 15 min) also exhibits two carbonyl vibrations, one at 2110 cm-1 and one at 2050 cm-1.
Anion/Cation Exchange Resin Tests.
This test was performed on both the iridium mixed silicotungstate and the iridium mixed phosphotungstate complex to demonstrate covalent support of the (COD)Ir+ moiety. A cation exchange column (7 mm×270 mm) was packed with Amberlyst A-15 resin which had been previously washed with aqueous Bu4 NOH until the pH of the wash solution remained strongly basic. Once packed, the column was washed with reagent grade acetonitrile. Roughly 0.1 g sample (i.e., the iridium mixed silicotungstate complex, the iridium mixed phosphotungstate complex, or [Ir(COD)(CH3 CN)2 ]BF4 as a control) dissolved in 1 ml of acetonitrile was placed at the top of the resin and eluted with acetonitrile at a rate of ca. 1 drop every 10 s. Analysis of the sample eluent showed that the solution passed through unchanged by the resin, while the control eluent indicated bonding of the cationic iridium.
An anion exchange column of similar proportions was packed with Amberlyst A-27 resin in the Cl- form and washed with reagent grade acetonitrile. Loading and elution were performed as described above and [Ir(COD)(CH3 CN)2 ]BF4 was again used as a control. Covalent bonding of the iridium to the heteropolyanion was verified by passing acetonitrile solutions of the two iridium polyoxoanion complex down the Amberlyst A-27 anion exchange column. The amber complexes (indicating the presence of the iridium polyoxoanion complexes) adhere tightly to the anion exchange resin while the control complex passes through the resin unaffected.
Hydrogenolysis of Coordinated COD to Yield Activated Iridium Mixed Silicotungstate Complex or Iridium Mixed Phosphotungstate Complex.
This reduction was carried out at room temperature by application of 40 psig hydrogen to a rapidly stirred acetones solution (see hydrogenations, general procedure) of either iridium mixed silicotungstate complex or iridium mixed phosphotungstate complex for 0.5-1 h. No free olefin is present in solution. The reduction is determined to be complete and the hydrogen vented, in the case of iridium mixed silicotungstate complex, when the appearance of black precipitate of (Ir(0))n is first observed. Since reduction of the polyoxoanion occurs with the iridium mixed phosphotungstate complex, hydrogenolysis is considered complete when the solution changes from yellow to green in color (due to formation of the heteropolyblue). Once exposed to air, the green acetone solutions of activated iridium mixed phosphotungstate complex rapidly turn back to the original yellow-amber color, indicating rapid oxidation of the heteropolyblue. In the presence of ≧100 eq cyclohexene, neither the iridium mixed silicotungstate complex nor the iridium mixed phosphotungstate complex react with hydrogen (after 48 h) to yield activated iridium mixed silicotungstate complex or iridium mixed phosphotungstate complex.
Since a small amount of (Ir(0))n precipitate is an unavoidable byproduct, the acetone solutions are filtered over Celite filter aid, to yield clear yellow to amber colored solutions, prior to removal of the solvent under vacuum. Drying under high vacuum at room temperature for 18 h yields the amorphous products described herein as activated iridium mixed silicotungstate complex and activated iridium mixed phosphotungstate complex.
The exact composition of these catalyst precursors (such as, e.g., Examples 5, 6, 7 and 8), which are formulated L'n Ir.heteropolyanion-y (where heteropolyanion=SiW9 Nb3 O407- or P2 W15 Nb3 O629-)) is unknown with respect to ligand L'.
Additionally, the IR spectrum of activated iridium mixed silicotungstate complex exhibits the same heteropoyanion characteristic bands found in the precatalyst iridium mixed solicotungstate complex, but the splitting of the intratriad M-O-M band has increased to 22 cm-1 in activated iridium mixed silicotungstate complex. Additionally, the M=O terminal oxygen band has shifted slightly to slightly higher energy (955 cm-1 for activated iridium mixed silicotunqstate complex, 952 cm-1 for iridium mixed silicotungstate complex). This result is consistent with the removal of surface electron density from the heteropolyanion upon activation of iridium mixed silicotungstate complex. The IR data suggest that controlled hydrogenolysis of iridium mixed silicotungstate complex (and by analogy iridium mixed phosphotungstate complex) leaves the Ir polyoxoanion moiety intact and slightly increases the bonding interaction between the iridium moiety and the intratriad bridging oxygens.
1 H NMR and IR spectra of CD3CN solutions of L'n Ir.P2 W15 Nb3 O628- fail to show any resonances or absorbances which can be attributed to hydride ligands. Reaction of acetonitrile solutions of Lx Ir.P2 W15 Nb3 O628- or Lx Ir.SiW9 Nb3 O406- with CCl4 does produce ≦2 eq CHCl3 (by GLC) but the quantity obtained is not reproducible. Other possibilities for L are coordinated acetone or acetone that has oxidatively added a C--H bond to the iridium. Such metallation of acidic C--H bonds by rhodium and iridium complexes are reported by English, A. D.; Herskovitz, J., J. Am Chem. Soc., 1977, 99, 1648.
During this hydrogenolysis step, Ir(1) is kinetically stabilized, with respect to reduction to Ir(0), by heteropolyanions with surface charge density, such as, e.g., SiW9 Nb3 O407 - and P2 W-5Nb3 O629-. To illustrate this point, one equivalent of the very low surface charge density heteropolyanion P2 W18 O626- .tbd.(PO4)26- (WO3)180 was added to one equivalent of Ir(COD)(CH3 CN)2 ]BF4 in acetone and the solution placed under 40 psig hydrogen. A black precipitate of (Ir(0))n formed within 5 minutes (Table 1, entry 3). If [Ir(COD)(CH3 CN)2 ]BF4 alone is treated with hydrogen, (Ir(0))n precipitates immediately. Thus, if the iridium mixed heteropolyoxoanion compounds can be regarded as reasonable models for oxide-supported metal catalysts (e.g., Ir/Al2 O3) then it is expected that basic sites on the oxide play a key role in the interaction between the support and the metal.
Although no loss in catalytic activity of activated iridium mixed silicotungstate complex has been observed when stored for up to 40 days as the dry solid (longer storage results in the appearance of a small amount of CH3 CN insoluble material), solutions of both activated complexes as well as dry, solid activated iridium mixed phosphotungstate complex do exhibit a loss of activity upon short term storage (≈2-3 h for solutions and ≈1-2 weeks for solid iridium mixed phosphotungstate complex). Consequently, solutions should be prepared immediately prior to use and storage of dry, solid activated iridium mixed phosphotungstate complex for periods longer than 1 should be avoided.
B. OLEFIN HYDROGENATIONS.
General Procedure. Catalytic hydrogenations of cyclohexene are done in Fischer-Porter pressure bottles equipped with high precision test gauges (either 0 to 60±0.09 psig or 0 to 100±0.15 psig). A dilute (typically 0.5mM) acetone solution (2.50 ml in volume) of the catalyst and 0.50 ml of freshly purified cyclohexene are placed in a 18×150mm borosilicate disposable test tube along with a small (≦1 cm in length) Teflon coated magnetic stir bar. The test tube is lowered into the Fischer-Porter bottle which is then capped, purged with hydrogen, and pressurized to 40 psig. The entire apparatus is clamped above a magnetic stirrer and the acetone/cyclohexene solution vigorously stirred. The reaction is monitored by recording the drop in hydrogen pressure as a function of time. At the completion of the hydrogenation, 1 H NMR (in CDCl3) is used to verify the extent of cyclohexene reduction and establish mass balance. The 1 H NMR integrals were verified by GLC to better than ±5%.
A new borosilicate test tube is used for each hydrogenation. Stir bars are periodically checked for contamination by running a blank (stir bar, acetone, and cyclohexene) and discarded if hydrogenation of cyclohexene is detected by 1 H NMR.
Kinetics, General Procedure. A kinetic analysis of the hydrogenation of cyclohexene catalyzed by activated iridium mixed silicotungstate complex is performed in a fashion nearly identical to the above hydrogenation procedure. The total volume of acetone and cyclohexene always equals 3.00 ml and the Fischer-Porter bottle is clamped in a thermostated water bath, held at 22°C, while the contents are stirred via a magnetic stirrer. The start of each hydrogenation is arbitrarily defined to occur after purging and pressurizing with hydrogen and commenced with immersion in the water bath. Reaction time is measured with an electronic timer with a precision of ±1 second.
Cyclohexene was measured with an appropriately sized gas tight syringe. The concentration of hydrogen is assumed to be proportional to Phydrogen.
The initial concentration of the activated iridium mixed silicotungstate complex is calculated by assuming a molecular weight of 4700 (this assumed value closely approximates the formulation (Bu4 N)6 [L2 Ir.SiW9 Nb3 O40 ]. Bu4 NBF4, where L=acetone). For (Ir(0))n, the number of active iridium sites is assumed to be equal to the number of Ir atoms present, except for the one sample with a known BET surface area, and it is assumed that all accessible iridium atoms are catalytically active. The assumptions result in calculated turnover frequency values and total number of turnovers which are very probably lower than the true values. The large amount of sample (generally ≧0.25 g) required for a BET surface area measurement precluded applying this technique to all samples of (Ir(0))n with the exception of one large batch (≈0.25 g) prepared by reducing 0.31 g [Ir(COD)(CH3 CN)2 ]BF4 with hydrogen. This sample gave a BET surface area of 2.57 m2 /g. The number of surface iridium atoms/g was calculated assuming that each Ir(0) atom (atomic radius of 1.36 Å) has a surface area of 5.81×10-20 m2.
Samples of low dispersion and ultradispersed Ir/Al2 O3 were subjected to hydrogen chemisorption. The results yield 7.9 and 80%, respectively.
Catalyst Recovery by Reaction with CO.
This reaction was carried out by splitting a solution of activated iridium mixed silicotungstate complex in acetone/cyclohexene (2.50 ml acetone, 0.50 ml cyclohexene, 0.5mM catalyst) into two portions. One portion was placed under 40 psig CO for 15 minutes while the other portion was placed under hydrogen (40 psig), as described above, until reduction of ≈500-25,000 eq cyclohexene was completed (by IH NMR). The solution was then vented and placed under 40 psig CO for 15 minutes. The IR spectrum was obtained, in the absorbance mode and using CaF2 solution cells (0.1 mm pathlength) referenced to CH3 CN, of both solutions. Comparison of the intensity of the carbonyl bands showed 100±5% conversion of the active catalyst to the carbonyl iridium mixed silicotungstate complex. The same procedure was applied to an acetone solution of activated iridium mixed phosphotungstate complex to provide an indication of the degree of catalyst conversion to the carbonyl iridium mixed phosphotungstate complex, with the same results.
General Catalyst Inhibition Tests.
A 0.5 mM 5:1 (v/v) acetone/cyclohexene solution (3.00 ml in volume) of active catalyst (activated iridium mixed silicotungstate complex or activated iridium mixed phosphotungstate complex), or the equivalent number of moles of (Ir(0))n or low dispersion and ultradispersed Ir/-Al2 O3, was prepared and exposed to 40 psig hydrogen, at 22°C, for a precisely measured (±1 s) period of time, not to exceed 0.5 h. 1 H NMR provided a measure of the extent of the hydrogenation and a plot of P hydrogen vs. time gave an indication of the change in reaction rate as a function of time. In all cases, the change in the slope of P hydrogen vs. time was negligible, hence the initial turnover frequency was approximated by the average turnover frequency. Then, a given number of equivalents of the reagent in question was added to the catalyst solution and the hydrogenation rate determined again, as described above. The results are presented in Table 2. Comparison of the initial hydrogenation rate before and after addition of the reagent in question provided a measure of the reagent's effectiveness as an inhibitor.
Hydrogenation of Benzene, Nitrobenzene, and 2,3-Dimethyl-2-butene.
These substrates were treated in the same manner as described above in the general olefin hydrogenation procedures, by successively substituting each for cyclohexene. The results are presented in Table 2.
Ligand Substitution Reactivity of Iridium Mixed Phosphotungstate Complex and [Ir(COD)(CH3 CN)2 ]BF4.
The lability of the COD ligand in either the iridium mixed phosphotungstate complex or [Ir(COD)(CH3 CN)2 ]+ with respect to displacement by 2,5-norbornadiene (NBD) Was investigated in room temperature acetone solution. Two, separate 1 ml solutions (0.02 M) of iridium mixed phosphotungstate complex and [Ir(COD)(CH3 CN)2 ]BF4 were prepared in CD3CN and the 1 H NMR obtained. Then, 0.15 ml NBD (1.4 mmol) was added to each solution and the 1 H NMR spectrum obtained, of both solutions, at arbitrary time intervals beginning with 5 min and ending with 3 h. For the solution containing [Ir(COD)(CH3 CN)2 ]BF4, both coordinated and free COD could be observed. However, only free COD was observed for the solution containing iridium mixed phosphotungstate complex. A comparison of the integration intensity of the olefinic protons for free COD as a function of time provided a qualitative measure of the relative rate of ligand substitution. The data indicate a five coordinate iridium phosphotungstate complex.
[Ir(COD)+]x :[SiW9 Nb3 O407- ]y Ratio vs. Rate Plot.
In order to determine the optimum [Ir(COD)+ ]x :[SiW9 Nb3 O407- ]y ratio, a plot of catalytic activity as a function of the ratio [Ir(COD)+ [x :[SiW9 Nb3 O407- ]y was constructed as follows: an acetone solution (6 ml in volume) containing 4.0 mg [Ir(COD)(CH3 CN)2 ]BF4 per each 1.00 ml of solution was prepared as described above. To each of 5 separate 1.00 ml aliquots was added a different quantity of (Bu4 N)7 SiW9 Nb3 O40 ranging from 0.78 to 2.0 eq and then the solvent was removed from each sample under vacuum, at room temperature, for 18 h. For each sample, hydrogenolysis of the coordinated COD to yield the active catalyst was accomplished as previously described. After drying (room temperature, high vacuum, 18 h), 2.50 ml dry acetone and 0.50 ml cyclohexane was added to each sample, followed by pressurizing to 40 psig with hydrogen. The rate of olefin hydrogenation was measured, as described under the general kinetics catalyst procedure, at 22° C. The results indicate that maximum stability and catalytic activity is obtained at a 1:1 [(COD)Ir+ ]:[SiW9 Nb3 O407- ] ratio.
Alternatively, excess (Bu4 N)7 SiW9 Nb3 O40 was added to a given amount of activated 1a to yield mixtures with an [Ir(COD)+ ]:SiW9 Nb3 O407- ] ratio <1. This method was used to check the results presented above.
At Ir(1) :SiW9 Nb3 O407- ratios of <1, (see Table 1, entry 2), the rate of catalysis decreases dramatically, whereas ratios >1 result in the rapid (<15 min) formation of (Ir(0))n, suggesting a supported, covalently bonded Ir(1) :SiW9 Nb3 O407- stoichiometry of 1:1. Thus, to avoid (Ir(0))n formation and to retain maximum hydrogenation rate, the system of choice is (Bu4 N)6 [(COD)Ir.SiW9 Nb3 O40 ] in acetone solution.
Olefin Hydrogenation.
The catalyst precursors iridium mixed phosphotungstate complex were preactivated by treatment of 0.01-0.02 M acetone solutions of either complex with 40 psig hydrogen for 0.1-1 hour at room temperature. Complete hydrogenation of the coordinate COD is demonstrated by the presence of 1.0±0.05 equivalents cyclooctane determined by GLC. Longer preactivation times or higher temperatures (50°C, 40 psig hydrogen, >10 min) lead to overreduction and Ir(0) formation (Table 1, entry 7), although the polyoxoanions in these complexes significantly inhibit this process.
A survey of the following variables was conducted with the goal of defining a reasonably optimum system for detailed studies: solvent (dry acetone, dry methyl ethyl ketone, propylene carbonate, hexafluoroacetone.3H2 O, dry acetonitrile, absolute ethanol, and 1,2-dichloroethane); platinumII, palladiumII, rhodiumI vs. iridiumI ; different polyoxoanions; and the optimum polyoxoanion:metal ratio. Acetone, iridium, the SiW9 Nb3 O407- heteropolyanion in the precursor complex, and a 1:1 Ir:polyoxoanion ratio emerged as the preferred embodiment. The optimized polyoxoanion-containing catalyst derived from the iridium mixed silicotungstate complex compares favorably with crabtree's homogeneous catalyst, [IrH2 (acetone)2 (PPH3)2 ]PF6, and heterogeneous ultradispersed Ir/η-Al2 O3. It exceeds the turnover rates for crabtree's catalyst by 2.2 fold and the maximum number of turnovers with Crabtree's catalyst by a factor of 31, while approaching the maximum turnover rate exhibited by the ultradispersed Ir/η-Al2 O3 catalyst (Table 1, entries 1, 5, and 8).
Significantly, SiW9 Nb3 O407- (as in the iridium mixed silicotungstate complex) and P2 W15 Nb3 O629- (as in the iridium mixed phosphotungstate complex) greatly inhibit the formation of Ir(0) precipitate. (Table 1, entries 1 and 2). For example, the iridium mixed silicotungstate complex remains as a clear, amber solution even after 25,000 turnovers over 48 hours. When either a polyoxoanion with very little anionic surface charge density was used ((Bu4 N)6 P2 W18 O62 =(Bu4 N [(P04)26- (W18 O54)0 ]; Table 1, entry 3), or no polyoxoanion was employed (Ir(COD(CH3 CN)2 ]BF4 alone; Table 1, entry 4), a grey/black precipitate indicating (Ir(0))n formed within 5 minutes. When 2 equivalents SiW9 Nb3 O407- per equivalent of Ir(COD)+ were preactivated and examined for catalytic activity, the rate was found to be half the hydrogenation rate obtained with the precatalyst iridium mixed silicotungstate complex (Table 1, entry 1a) while an excess of Ir(COD)+ with respect to SiW9 Nb3 O407- resulted in formation of (Ir(0))n, indicating an optimum Ir:polyoxoanion ratio of 1:1.
An exceedingly powerful probe of homogeneous-soluble catalytic reactions is chemical kinetics. Indeed, this approach is expected to discern between catalysis by a discrete, molecular heteropolyanion-supported iridium complex (such as the formulation proposed for activated iridium mixed silicotungstate complex) and catalysis by other species which perhaps form under hydrogenation conditions (i.e., agglomerated iridium. It is unlikely that the active catalyst is of the general form "Iry [SiW9 Nb3 O407- ]x ", y≠x, since greater than 1 equivalent of SiW9 Nb3 O407- inhibits catalysis and the catalyst has been shown to be anionic). The former case should produce kinetics which are reproducible and first order in catalyst. On the other hand, the latter case would be suspect if any of the following characteristics were observed; an initial induction period, irreproducible rates, or non-first order dependence on catalyst.
The kinetic analysis of cyclohexene hydrogenation, catalyzed by activated iridium mixed silicotungstate complex (activated iridium mixed phosphotungstate was not kinetically investigated due to the competition between olefin hydrogenation and heteropolyanion reduction) at 22° C., and encompassing several different batches of catalyst, has provided the following results: First, under all combinations of initial [cyclohexene], [catalyst], and initial Phydrogen examined, there was no observable induction period as indicated by a plot of Phydrogen vs. time, of which a representative example is shown in FIG. 1.
Second, a gentle curvature of these plots (our FIG. 1A) is indicative of rate dependence on [H2 ]and/or [cyclohexene]. Furthermore, plotting the initial turnover frequency vs. either initial Phydrogen (and [H2 ]), FIG. 1c or [catalyst], FIG. 2, yields a straight line of slope=1 and intercept=0, thus the mechanism is first order in both H2 and catalyst. Similar treatment of initial turnover frequency at various [cyclohexene] shows saturation kinetics at [cyclohexene] 1.0 M. At [cyclohexene] <1.0 M, initial rates cannot be accurately determined with the apparatus described herein.
Third, initial rate values, expressed as turnover frequency, are remarkably reproducible (±15%) even for different batches of activated iridium mixed silicotungstate complex. Such a high degree of reproducibility has not been obtained with (Ir(0))n (from overreduced iridium mixed silicotungstate complex or overreduced [Ir(COD)(CH3 CN)2 ]BF4) as expected. Typical error bars are ±30-50% for material obtained from a single preparation while samples from different preparations have given apparent turnover frequencies (uncorrected for surface area) ranging from 50 to 3100 h-1.
Due to the poor degree of reproducibility of initial hydrogenation rates catalyzed by (Ir(0))n, a kinetic analysis of this system does not yield readily interpreted results. For example, changing the initial hydrogen pressure from 20-65 psig does not result in a significant (greater than experimental error) change in the initial turnover frequency (the same is true for changes (from 1.00-4.95 M) in the initial olefin concentration). However, a plot of Phydrogen vs. time for cyclohexene hydrogenations catalyzed by (Ir(0))n yields a straight line for at least four half lives (FIG. 1a) indicating zero order dependence on [H2 ] and [cyclohexene]. These results show a significant difference between hydrogenations catalyzed by activated iridium mixed silicotungstate complex and (Ir(0))n. This kinetic analysis demands that the two catalyst system, activated iridium mixed silicotungstate complex and (Ir(0))n, are different chemical entities.
In comparison, 80% dispersed 1%-Ir/n-Al2 O3 exhibits zero order dependence on olefin during the first three half lives if the hydrogen pressure is kept above 25 psig (See FIG. 1B). However, dependence on [H2 ] is observed when the hydrogen pressure drops below 25 psig, even at less than three half lives.
Overall the results are definitive in establishing that the polyoxoanion significantly affects the hydrogenation rate, the total number of turnovers, and the tendency to form an (Ir(0))n precipitate.
Preparation of, and Ion Exchange Experiments with,
(Bu4 N)6 [(COD)Ir..SiW9 V3O40 ]
An aetonitrile solution (10 ml) of 868 mg, 0.208 mmol, (Bu4 N)7 SiW9 V3 O40 (See Finke, R. G.; Rapko, B.; Domaille, P. J.; Organomet. 1986, 5, 175) was added, with stirring, to an acetonitrile solution (5-10 ml) containing 100 mg, 0.208 mmol, [Ir(COD)(CH3 CN)2 ]BF4 to produce (Bu4 N)6 [(COD)Ir.SiW9 V3O40 ] as a green product. The solvents were removed under vacuum and the green solid was dried at room temperature, <0.3 torr vacuum, for 16 hours.
To verify that the (COD)Ir+ moiety is covalently bonded to the SiW9 V3O407- moiety, a green acetonitrile solution of (Bu4 N)6 [(COD)Ir.SiW9 V3 O40 ] was loaded onto first a cation exchange column (Amberlyst A-15 resin) and then an anion exchange column (Amberlyst A-27 resin) and slowly eluted with acetonitrile. The green complex moved through the cation exchange resin with the advancing solvent front, but adhered tightly to the anion exchange column, consistent with the overall anionic charge for the support complex [(COD)Ir.SiW9 V3O40 ]6-.
Preparation of, and Ion Exchange Experiments with, (Bu4 N)8 [(COD)Ir..P2 W15 V3 O62 ]
An acetonitrile solution (10 ml) containing 1.279 g, 0.208 mmol, (Bu4 N)9 P2 W15 V3 O62 (See Finke, R. G.; Rapko, B.; Saxton, R. J.; Domaille, P. J.; J. Am. Chem. Soc. 1986, 108, 2947) was added, with stirring, to an acetonitrile solution (5-10 ml) of 100 mg., 0.208 mmol, [Ir(COD)(CH3 CN2 ]BF4. The solvents were removed under vacuum followed by 16 hours drying at room temperature and <0.3 torr vacuum to yield a green solid formulated as (Bu4 N)8 [(COD)Ir.P2 W15 V3 O62 ].
Ion exchange experiments, analogous to those described above, were performed with (Bu4 N)8 [(COD)Ir.P2 W15 V3 O62 ]. The results (tight bonding of the orange complex to anion exchange resin, no interaction with cation exchange resin) are consistent with covalent bonding between (COD)Ir+ and P2 W15 V3 O629- to yield the overall anionic complex [(COD)Ir.P2 W15 V3 O62 ]8-.
An acetone solution of 2.2 mg (0.00469 mmol) [Ir(COD)(CH3 CN)2 ]BF4 was freshly prepared in a N2 glove bag as described in Example 4. To this solution was added 18.1 mg (Bu4 N)4 SiW12 O40 (0.00469 mmol) and 0.50mL (4.94 mmol) cyclohexene, and the solution was then placed inside a pressure vessel for catalytic hydrogenation testing (these manipulations were also done inside of the N2 -filled glove bag). After capping, the pressure vessel containing the [Ir(COD)(CH3 CN)2 ]+ and SiW12 O404- was removed from the glove bag and pressurized to 40 psig with H2. The vessel was then placed in a 22°C controlled-temperature water bath.
Within 5 minutes the solution was black and contained a very finely divided black precipitate (presumably Ir(0)). After 0.50 hr the pressure had decreased by 5.8 psig and 1 H NMR indicated 72% hydrogenation to cyclohexane. This high hydrogenation rate of 1510 turnovers/h, taken with the appearance of a black precipitate, is most consistent with the rapid formation of Ir(0) precipitate.
Effect of Solvent on the Catalytic Activity of [Ln Ir..Heteropolyanion]y- (Heteropolyanion=SiW9 Nb3 O407-, y=6; and P2 W15 Nb3 O629-, y=8) and Urabe's Catalyst (RhCl(PPh3)3 plus SiW12 O404-).
The optimum solvent for catalytic hydrogenation of cyclohexene with catalysts derived by activation of the precursors [Ln.SiW9 M3 O40 ]6- and Ln.P2 W15 M3 O62 ]8- (M=VV, NbV) is acetone. In this solvent the initial hydrogenation rate with catalytically activated ([Ln ∼SiW9 Nb3 O40 ]6- is 1150 turnovers/hr (see Example 20). The iridium mixed phosphotungstate and iridium mixed silicotungstate catalyst precursors are insoluble in benzene and similar non-polar solvents and consequently exhibit no catalytic activity in these solvents.
In contrast, Urabe's catalyst system, an equal
molar mixture of RhCl(PPh3)3 and SiW12 O404-, is very active in benzene but inactive in acetone. For example, 1.15 mg (0.00124 mmol) RhCl(PPh3)3 and 4.73 mg (0.00123 mmol) (Bu4 N)4 SiW12 O40 dissolved slowly in a mixture of 2.50 mL benzene and 0.50 mL (4.94 mmol) cyclohexene. The solution was placed under 40 psig H2 in a glass pressure vessel equipped with a pressure gauge accurate to +/-0.09 psig. The vessel was placed in a controlled-temperature water bath at 22°C and stirred vigorously.
The H2 pressure was monitored as a function of time. After 0.611 hr the pressure had decreased by 0.9 psig and 1 H NMR confirmed that a portion of the cyclohexene had been hydrogenated. Comparison of the integrated area of the cyclohexane proton peak to the integrated area of the cyclohexene olefinic proton peaks provided a determination of the extent of hydrogenation; 7% in this case. The average turnover rate is then calculated to be 470 turnovers/hr.
This experiment was repeated by dissolving 3.41 mg (0.00368 mmol) RhCl(PPh3)3 and 14.03 mg (0.00365 mmol) (Bu4 N)4 SiW12 O40 in a mixture of 2.50 mL acetone and 0.50 mL cyclohexene (solutes dissolved rapidly as opposed to the slow dissolution in the benzene solution). No hydrogenation had occurred (by H2 pressure drop or 1 H NMR) after 0.500 hr indicating essentially no catalytic activity in acetone.
Effect of Added SiW12 O404- on the Catalytic Activity of Urabe's Catalyst.
To the catalytically active benzene solution of 1.15 mg RhCl(PPh3)3 and 4.73 mg (Bu4 N)4 SiW12 O40, prepared as described above in Example 24, was added an additional 5.34 mg (0.00124 mmol) (Bu4 N)4 SiW12 O40. The H2 pressure was restored to 40 psig and the pressure monitored as a function of time. After 0.833 hr the pressure had decreased by 1.3 psig and 1 H NMR indicated (by the method described in Example 24) that an additional 9% hydrogenation of the cyclohexene had occurred. The average turnover rate then, for the
catalyst after addition of SiW12 O404- (to give a total of 2 equivalents SiW12 O404-), was 405 turnovers/hr. This value is probably not significantly different from the average turnover rate with one equivalent of SiW12 O404-.
This result is in marked contrast to the effect of additional equivalents of the basic heteropolyanion SiW9 Nb3 O407- on the catalytic activity of the iridium mixed silicotungstate complex (see Examples 19 and 20), and suggests a weak rather than a strong (covalent) chemical interaction between RhCl(PPh3)3 and SiW12 O404-.
Control Experiment Demonstrating a Lack of Covalent Bonding Between RhCl(PPh3)3 and SiW12 O404-.
To check the hypothesis that only weak (non-covalent) chemical interactions are shared by RhCl(PPh3)3 and SiW12 O404-, the catalytically-active benzene solution containing Urabe's catalyst, prepared as described in Example 25, was subjected to the ion-exchange test (see Examples 12, 21, and 22). Thus, Amberlyst A-15 cation exchange resin (about 0.5 mL in volume; previously washed with aqueous Bu4 NOH, then distilled water, then acetone) was added to the catalytically-active benzene solution of RhCl(PPh3)3 and SiW12 O404-, and the H2 pressure restored to 40 psig. Addition of the ion exchange resin was done on the bench top by ceasing to stir the catalyst solution, quickly opening the pressure vessel, adding the ion-exchange resin, closing the vessel, and immediately purging 5-10 times with H2 prior to reinstating vigorous stirring of the solution. This technique did not allow sufficient air into the catalyst solution to significantly alter catalytic activity (as determined by experiments in which the catalytic activity of the iridium mixed silicotungstate was unaffected, see below).
After 0.25 hr the yellow-orange color of the solution was taken up by the cation exchange resin, indicating removal of the RhI from the solution. One half hour after addition of the cation exchange resin no additional hydrogenation had occurred, consistent with the removal of the catalytically active RhI from solution.
Repeating this experiment with a catalytically active solution of the iridium mixed silicotungstate (0.00185 mmol based on the catalyst precursor) in 2.50 mL acetone and 0.50 mL cyclohexene (4.94 mmol) gave the following observations. Addition of about 0.5 mL in volume of the cation exchange resin Amberlyst A-15 (in the Bu4 N+-loaded form, washed with acetone), followed by stirring under 40 psig H2 for 0.50 hr had no effect on the color of the solution or the hydrogenation rate (still 1150 turnovers/hr).
However, addition of Amberlyst A-27 anion exchange resin (loaded in the Cl- form, washed with acetone) to a similar solution, followed by pressurizing to 40 psig with hydrogen, resulted in loss of color of the solution in 15 min. The catalytic activity of the solution also decreased significantly; this experiment was repeated three times and the catalytic activity after treatment with anion exchange resin decreased to 10% of the initial rate (i.e., 0-110 turnovers/hr).
These results are consistent with covalent bonding of the Ir(1) moiety to the basic polyoxoanion SiW9 Nb3 O407- resulting in an anionic catalyst. Whereas Urabe's catalyst system is lacking this covalent bonding interaction between RhI and the non-basic polyoxoanion SiW12 O404-, the catalyst is the cationic RhI complex.
While the invention has been described with reference to particularly preferred embodiments, it will be apparent to those skilled in the art that other variations are possible which are still within the scope of the appended claims.
| TABLE 1 |
| __________________________________________________________________________ |
| Appearance Maximum No. |
| Upon Initial Turnover |
| of Turnovers |
| Entry |
| Precatalyst H2 Addition |
| Frequencya (22°C) |
| Demonstrated |
| __________________________________________________________________________ |
| 1a [L'n Ir · SiW9 Nb3 O40 ]7- |
| Clear amber |
| 1150 ± 175 |
| 25,500 |
| soln. |
| 1b [L'n Ir · SiW9 Nb3 O40 ]7 |
| Clear amber |
| 550 ± 80 |
| -- |
| 1 eq. (Bu4 N)7 SiW9 |
| soln. |
| Nb3 O40 |
| 2 [L'n Ir · P2 W15 Nb3 O62 ]9- |
| Clear amber |
| 480 ± 75 |
| 2,550 |
| 3 Ir(COD)CH3 CN)2+ BF4- + |
| Grey/blk. ppt. |
| 1050-1600b |
| -- |
| (Bu4 N)6 P2 W18 O62 |
| forms within |
| 5 min. |
| 4 Ir(COD)CH3 CN)2+ BF4- |
| Grey/blk. |
| 3400-4500c |
| 51,600 |
| ppt. forms |
| immediately |
| 5 IrH2 S2 (PPH3)2+ PF6- |
| Clear pale |
| 530 ± 80d |
| 810 |
| S = acetone yellow soln. |
| 6 Low Dispersion |
| Grey suspen- |
| 3900 ± 1000 |
| 410,000 |
| Ir/γ-Al2 O3 |
| sion |
| 7 Overreduced Amber soln. |
| 1750-2780b |
| 15,000 |
| [L'2 Ir · SiW9 Nb3 O40 ]7- |
| with blk. ppt. |
| (40 psig H2, 22°C, 2 hrs) |
| 8 Ultradispersed |
| Grey suspen- |
| 1740 ± 300 |
| -- |
| Ir/η-Al2 O3 |
| sion |
| __________________________________________________________________________ |
| a Expressed as mol product · mol catalyst-1 · |
| h-1 |
| b The surface area of the (Ir(0))n precipitate in these |
| entries is unknown and probably varies greatly with sample preparation. |
| Consequently, turnover frequencies are calculated assuming that all the I |
| present is catalytically active which is surely not true. Hence, these |
| values represent lower limits while the true value may be ≧4500 |
| turnsover/h, assuming similar surface area and activity as entry 4. BET |
| surface area measurements were not obtained on these samples due to the |
| large amount of material required for analysis. |
| c The turnover frequency and total number of turnovers were |
| calculated for a sample of Ir(0) for which both the BET surface area |
| and hydrogenation rate data had been obtained. Different batches of |
| (Ir(0))n prepared from overreduction of [(Ir(COD)(CH3 |
| CN)2 ]BF4 show vastly different hydrogenation rates (values, |
| uncorrected for surface area, range from 50-1600 turnovers/h) which |
| probably reflects a large variation in the surface area of the |
| precipitated metal. |
| d Inactive in acetone (as previously reported) and most active in |
| chlorinated hydrocarbon solvents; therefore, 1,2dichloroethane was used a |
| solvent for this entry only. turnsover/h, assuming similar surface area |
| and activity as entry 4. BET surface area measurements were not obtained |
| on these samples due to the large amount of material required for |
| analysis. c) The turnover frequency and total number of turnovers were |
| calculated for a sample of Ir(0) for which both the BET surface area |
| and hydrogenation rate data had been obtained. Different batches of |
| (Ir(0))n prepared from overreduction of [(Ir(COD)(CH3 |
| CN)2 ]BF4 show vastly different hydrogenation rates (values, |
| uncorrected for surface area, range from 50-1600 turnovers/h) which |
| probably reflects a large variation in the surface area of the |
| precipitated metal. d) Inactive in acetone (as previously reported) and |
| most active in chlorinated hydrocarbon solvents; therefore, |
| 1,2-dichloroethane was used as solvent for this entry only. |
| TABLE 2 |
| __________________________________________________________________________ |
| Catalyst |
| Low Dispersion |
| Ultradispersed |
| Testa Activated 1 |
| (IR(0))n |
| 1%-Ir/γ-Al2 O3 |
| 1%-Ir/η-Al2 O3 |
| __________________________________________________________________________ |
| CO Inhibitor |
| Inhibitor |
| Inhibitor |
| Inhibitor |
| Anion Exchange |
| Inhibitor |
| No Effect |
| No Effect |
| No Effect |
| Resin |
| COD Inhibitor |
| No Effect |
| No Effect |
| Inhibitor |
| CH3 CN Inhibitor |
| No Effect |
| No Effect |
| Inhibitor |
| Et3 N Inhibitor |
| No Effect |
| No Effect |
| -- |
| 2.0 eq PPh3c |
| 2.0 ± 0.1 |
| -- 1.5 <<0.35 |
| Air Inhibitor |
| No Effect |
| No Effect |
| Inhibitor |
| PhNO2d |
| Not Reduced |
| 15% Reduced |
| 16% Reduced |
| Not Reduced |
| to Aniline |
| to Aniline |
| Benzened |
| Not Reduced |
| 5% Reduced to |
| 5% Reduced to |
| Not Reduced |
| Cyclohexane |
| Cyclohexane |
| 2,3-Dimethyl- |
| Not Reduced |
| 55% Reduced |
| 48% Reduced |
| 30% Reduced |
| 2-Butened to Dimethyl- |
| to Dimethyl- |
| to Dimethyl- |
| butane butane butane |
| Reproducibility ± 15% |
| ±35%e |
| -- -- |
| of Kinetics |
| Max No. of 25,500 51,600 410,000 -- |
| Turnoversc |
| __________________________________________________________________________ |
| a See text for a description of these classification tests and |
| results. |
| b CO treatment of activated 1 results in 100 ± 5% recovery of |
| iridium as the dicarbonyl 3. |
| c Equivalents required to completely inhibit catalytic activity. |
| d Product yields were measured by 1 H NMR after 2 hours reaction |
| time. Not reduced means no product was detected. |
| e This degree of reproducibility (±35%) could only be obtained |
| within a given batch of (Ir(0))n. Reproducibility between |
| different batches was ±95% (see footnote C, Table 1). |
| TABLE 3 |
| ______________________________________ |
| Polyoxoanion and Solvent Variations for the Olefin Hydrogena- |
| tion Hydrogenation Catalyst System [Lx Ir.(polyoxoanion)]n |
| Hydrogenation |
| Solvent Polyoxoanion Ratea |
| ______________________________________ |
| 1,2-dichloroethane |
| (Bu4 N)7 SiW9 Nb3 O40 |
| Inactive |
| Me2 SO (Bu4 N)7 SiW9 Nb3 O40 |
| Inactive |
| THF (Bu4 N)7 SiW9 Nb3 O40 |
| 80 Turnovers/h |
| EtOH (Bu4 N)7 SiW9 Nb3 O40 |
| 100 Turnovers/h |
| CH3 CN (Bu4 N)7 SiW9 Nb3 O40 |
| 210 Turnovers/h |
| MeC(O)Et (Bu4 N)7 SiW9 Nb3 O40 |
| 530 Turnovers/h |
| Propylene Carbonate |
| (Bu4 N)7 SiW9 Nb3 O40 |
| 285 Turnovers/h |
| Acetone (Bu4 N)7 SiW9 Nb3 O40 |
| 1150 Turnovers/h |
| Acetone (Bu4 N)9 P2 W15 Nb3 O62 |
| 480 Turnovers/h |
| Acetone (Bu4 N)7 SiW9 V3 O40 |
| Inactive |
| Acetone (Bu4 N)9 P2 W15 V3 O62 |
| Inactive |
| ______________________________________ |
| a Initial rate for the catalytic hydrogenation of cyclohexene at |
| 22°C and an initial hydrogen pressure of 40 psig. |
Edlund, David J., Saxton, Robert J., Finke, Richard G.
| Patent | Priority | Assignee | Title |
| 5250739, | Mar 20 1992 | CATALYTICA ADVANCED TECHNOLOGIES, INC | Process for catalytically oxidizing cycloolefins, particularly cyclohexene |
| 6005148, | Dec 23 1996 | Seton Hall University | Supported catalysts |
| 6025295, | Dec 23 1996 | SETON HALL, UNIVERSITY | Supported catalysts |
| 6040262, | Mar 10 1998 | BP Chemicals Limited | Catalyst and use thereof |
| 6136746, | Jun 11 1998 | Seton Hall University | Poly-oxyanions as anchoring agents for metal complexes |
| Patent | Priority | Assignee | Title |
| 4294989, | Sep 09 1968 | Monsanto Company | Methylcyclohexyl-O-anisylphosphine |
| 4720474, | Sep 24 1985 | CATALYTICA ASSOCIATES, A CALIFORNIA LIMITED PARTNERSHIP | Olefin oxidation catalyst system |
| 4853357, | Sep 24 1985 | Catalytica Associates | Olefin oxidation catalyst system |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Oct 10 1988 | EDLUND, DAVID J | UNIVERSITY OF OREGON, THE | ASSIGNMENT OF ASSIGNORS INTEREST | 005151 | /0663 | |
| Oct 10 1988 | FINKE, RICHARD G | UNIVERSITY OF OREGON, THE | ASSIGNMENT OF ASSIGNORS INTEREST | 005151 | /0663 | |
| Oct 19 1988 | SAXTON, ROBERT J | UNIVERSITY OF OREGON, THE | ASSIGNMENT OF ASSIGNORS INTEREST | 005151 | /0663 | |
| Oct 26 1988 | The University of Oregon | (assignment on the face of the patent) | / | |||
| Jun 01 1994 | OREGON, UNIVERSITY OF | ENERGY, DEPARTMENT, UNITED STATES | CONFIRMATORY LICENSE SEE DOCUMENT FOR DETAILS | 007764 | /0526 |
| Date | Maintenance Fee Events |
| Aug 07 1992 | ASPN: Payor Number Assigned. |
| Aug 07 1992 | RMPN: Payer Number De-assigned. |
| Aug 10 1992 | ASPN: Payor Number Assigned. |
| Nov 17 1995 | M283: Payment of Maintenance Fee, 4th Yr, Small Entity. |
| Dec 21 1999 | REM: Maintenance Fee Reminder Mailed. |
| May 26 2000 | M286: Surcharge for late Payment, Small Entity. |
| May 26 2000 | M284: Payment of Maintenance Fee, 8th Yr, Small Entity. |
| May 26 2000 | ASPN: Payor Number Assigned. |
| Jun 01 2000 | RMPN: Payer Number De-assigned. |
| Dec 10 2003 | REM: Maintenance Fee Reminder Mailed. |
| May 26 2004 | EXP: Patent Expired for Failure to Pay Maintenance Fees. |
| Date | Maintenance Schedule |
| May 26 1995 | 4 years fee payment window open |
| Nov 26 1995 | 6 months grace period start (w surcharge) |
| May 26 1996 | patent expiry (for year 4) |
| May 26 1998 | 2 years to revive unintentionally abandoned end. (for year 4) |
| May 26 1999 | 8 years fee payment window open |
| Nov 26 1999 | 6 months grace period start (w surcharge) |
| May 26 2000 | patent expiry (for year 8) |
| May 26 2002 | 2 years to revive unintentionally abandoned end. (for year 8) |
| May 26 2003 | 12 years fee payment window open |
| Nov 26 2003 | 6 months grace period start (w surcharge) |
| May 26 2004 | patent expiry (for year 12) |
| May 26 2006 | 2 years to revive unintentionally abandoned end. (for year 12) |